CN105417585B - The preparation method of heavy mangano-manganic oxide - Google Patents
The preparation method of heavy mangano-manganic oxide Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of heavy mangano-manganic oxide, it is that manganese salt solution is precipitated as solid oxalic acid manganese with sodium oxalate solution, then manganese oxalate is made to change into manganous hydroxide toward dropwise addition sodium hydroxide solution in manganese oxalate slurries, it is 6.5~7.5 to control the pH value of reaction system, while be passed through air is oxidized to heavy mangano-manganic oxide by manganous hydroxide.Chemical equation is：Mn2++Na2C2O4=MnC2O4+2Na+；MnC2O4+ 2NaOH=Mn (OH)2+Na2C2O4；6Mn(OH)2+O2=2Mn3O4+6H2O.Present invention process is simple, environment-friendly, easily operated, does not have basic salt or other Mn oxides to generate, overcome pH when prior art manganese salt oxidation prepares heavy mangano-manganic oxide cannot precise control problem.The generation of manganous hydroxide and be oxidized to mangano-manganic oxide speed it is very slow, be conducive to growing up for mangano-manganic oxide crystal, the heavy mangano-manganic oxide sulfur content of production is low, average grain diameter be 5~6 μm, product tap density be more than 2.0g/cm3, more than 71.5%, sulfate radical content is less than 0.02% to Mn contents, fully meets the requirement of the lithium cell anode material lithium manganate for preparing high-rate charge-discharge capability.
Description
Technical field
The present invention relates to a kind of preparation method of heavy mangano-manganic oxide, in particular for preparing anode material of lithium battery manganese
The preparation method of the heavy mangano-manganic oxide of sour lithium.
Background technology
Mn3O4It is a kind of Mn oxide of stabilization, mainly for the preparation of MnZn iron soft magnetic materials, is widely used in various electronics
The manufacture of element, is the basic material of the industries such as electromechanics, electronics, information, is widely used in electromagnetism storage device.Four oxygen
It is also a kind of important source material of synthetic lithium manganate to change three manganese, due to Mn3O4With with LiMn2O4Identical spinel structure, uses
Mn3O4LiMn is prepared as presoma sintering2O4The time of crystal transfer can be reduced, the time of solid-phase sintering is greatly shortened.Mangaic acid
The lithium mangano-manganic oxide huge market demand, application prospect is wide, is just being increasingly subject to people's attention.
The method for producing mangano-manganic oxide has manganese salt or Mn oxide high-temperature decomposition, manganese powder air oxidation process, manganese
The methods such as salt wet oxidation.Manganese salt or Mn oxide pyrolytic directly prepare Mn3O4, with low cost, high-temperature calcination technique
Simply, product capacity is low when the mangano-manganic oxide that the easily controllable advantage of process, but high-temperature calcination is obtained prepares LiMn2O4 and follows
Ring performance is not good, is not suitable for the production of anode material of lithium battery LiMn2O4.Electrolytic metal manganese powder suspension oxidizing process be with
Electrolytic manganese metal is raw material, and suspension is made by the way that manganese piece is crushed, and is oxidant using air or oxygen, in uniform temperature and
Mangano-manganic oxide is prepared under additive concentration.With manganese powder under the conditions of ammonia air oxidation produce mangano-manganic oxide, its
Microscopic appearance is cotton-shaped, and apparent gravity is small, tap density about 1.2g/cm3, impurity content is high, can not meet lithium battery anode material
The requirement of material LiMn2O4 production.
Manganese salt wet oxidation method is to prepare a kind of mangano-manganic oxide development method faster at present, i.e., in manganese sulfate solution
Alkaline matter is added, manganese salt is converted into manganous hydroxide (Mn (OH)2), then aoxidize solution with oxidant, oxygen or air
Middle manganous hydroxide, so that mangano-manganic oxide is obtained.Publication number CN101948138A, CN103570072A, CN101898797A,
The Chinese invention patent of CN103739018A, CN101066780A is described with manganese sulfate as raw material, with NaOH, hydroxide
Potassium or ammoniacal liquor prepare presoma manganous hydroxide for precipitating reagent, then prepare mangano-manganic oxide with air, oxygen or hydrogen peroxide oxidation,
The method avoids the generation of alkali formula manganese sulfate, the mangano-manganic oxide sulfur content of preparation is low, but because manganous hydroxide is oxidized speed
Degree is very fast, and nucleus formation speed is much larger than rate of crystalline growth, therefore is hardly produced hyperbaric mangano-manganic oxide product（It is logical
Often it is also referred to as heavy mangano-manganic oxide）.The Chinese patent of publication number CN102491422A, CN102730762A discloses free
Mn2+The method that mangano-manganic oxide is prepared through air or oxygen oxidation, the method flow is short, can prepare hyperbaric four oxidation three
Manganese, but need to add manganese salt and alkali lye simultaneously in oxidizing process, and the strictly charging rate and ratio of control manganese salt and alkali lye
Example, it is ensured that the pH value of solution generally uses ammoniacal liquor as pH buffer between 6~8, not only technological operation is stranded this method
Difficulty, ammoniacal liquor volatilization also deteriorates operating environment, if operation is not tight, easily generates alkali formula manganese sulfate or other Mn oxides,
Form mixed crystal, reduce Mn3O4Quality, it is difficult to meet anode material of lithium battery LiMn2O4 production requirement.
The content of the invention
It is first with water that soluble manganous salt is molten it is an object of the invention to provide the preparation method of heavy mangano-manganic oxide
Solution is configured to manganese salt solution, sodium oxalate dissolving is configured to sodium oxalate solution, by NaOH dissolving, to be configured to NaOH molten
Liquid.Then manganese salt solution and sodium oxalate solution carry out precipitation reaction generation solid oxalic acid manganese, with water by solid after filtering, washing
Manganese oxalate is deployed into manganese oxalate slurries, then manganese oxalate is changed into hydrogen toward being slowly added dropwise sodium hydroxide solution in manganese oxalate slurries
Manganese oxide, it is 6.5~7.5 to control the pH value of reaction system, and being passed through air while sodium hydroxide solution is added dropwise is aoxidized
Reaction, heavy mangano-manganic oxide is oxidized to by manganous hydroxide.Filtered after the completion of oxidation reaction, washed, dried, that is, obtain heavy four
Mn 3 O product.Chemical equation is：
Mn2++Na2C2O4=MnC2O4+2Na+
MnC2O4+2NaOH=Mn(OH)2+Na2C2O4
6Mn(OH)2+ O2=2Mn3O4+6H2O
The method that the present invention prepares heavy mangano-manganic oxide, comprises the following steps：
Step one：By soluble manganous salt pure water or deionized water dissolving, the manganese salt for being configured to 0.5~2mol/L is molten
Liquid；Sodium oxalate pure water or deionized water dissolving are configured to the sodium oxalate solution of 0.2~0.4mol/L；By NaOH with pure
Water or deionized water dissolving are configured to the sodium hydroxide solution of 0.5~5mol/L；
Step 2：The manganese salt solution that step one is obtained is added in sodium oxalate solution, by rubbing for manganese ion and sodium oxalate
You feed intake than the ratio for 1: 1 and carry out precipitation reaction, and controlling reaction temperature is 40 DEG C~90 DEG C, and manganese salt solution feed time 10~
120min, adds 30~60min of insulation reaction after material, is filtered after the completion of reaction, washed, and obtains solid oxalic acid manganese；
Step 3：Step 2 gained solid oxalic acid manganese pure water or deionized water are slurried, solid oxalic acid manganese and water
Quality liquid-solid ratio be 5~10:1.Under agitation toward being slowly added continuously step in manganese oxalate slurries（1）Prepare
Sodium hydroxide solution, makes manganese oxalate change into manganous hydroxide.The sodium oxalate solution of manganese oxalate and NaOH reaction by-product can be with
Recycle.
NaOH is 2: 1 with the molar ratio of manganese oxalate.The pH value for controlling reaction system is 6.5~7.5.Hydroxide
20~40h of sodium solution charging reaction time, 30 DEG C~90 DEG C of reaction temperature.Air is passed through while sodium hydroxide solution is added dropwise
Oxidation reaction is carried out, manganous hydroxide is oxidized to heavy mangano-manganic oxide.Air mass flow is 0.1~0.5M3/h.Material all adds
Continue to react 3~6h after complete.Filtered after the completion of oxidation reaction, washed, dried, that is, obtain heavy mangano-manganic oxide product.Obtain
Heavy mangano-manganic oxide product average grain diameter be 5 ~ 6 μm, tap density be more than 2.0g/cm3, Mn contents be more than 71.5%, sulfuric acid
Radical content is less than 0.02%.
Heretofore described soluble manganous salt is any one in manganese sulfate or manganese nitrate, manganese chloride；Oxalic acid
Sodium is the industrial ethanedioic acid sodium of main content 99.5% or the by-product sodium oxalate solution of step 3；NaOH is the industry of main content 96%
The industrial liquid NaOH of solid sodium hydroxide or main content 30%.
It is simple production process of the present invention, environment-friendly, easily operated, by controlling sodium hydroxide solution rate of addition, very
Easily the pH of reaction system is controlled 6.5~7.5, basic salt or the generation of other Mn oxides are not had, overcome existing skill
When art manganese salt oxidation prepares heavy mangano-manganic oxide pH cannot precise control problem.The generation of manganous hydroxide and it is oxidized to four
The speed of Mn 3 O is very slow, is conducive to growing up for mangano-manganic oxide crystal, and the heavy mangano-manganic oxide sulfur content of production is low, puts down
Equal particle diameter is 5 ~ 6 μm, and product tap density is more than 2.0g/cm3, more than 71.5%, sulfate radical content is less than 0. 02% to Mn contents,
Fully meet the requirement of the lithium cell anode material lithium manganate for preparing high-rate charge-discharge capability.
Embodiment 1
Manganese sulfate is dissolved in pure water or deionized water is configured to the manganese sulfate solution that 2L concentration is 0.5mol/L, by sodium oxalate
The sodium oxalate solution that 2.5L concentration is 0.4mol/L is configured to pure water or deionized water, under agitation by manganese sulfate solution
It is added in sodium oxalate solution, keeps 80 DEG C of reaction temperature, feed time 60min adds the follow-up continuous insulation reaction 30min of material,
Filtered after the completion of reaction, washed, obtain manganese oxalate solid.
Above-mentioned manganese oxalate solid pure water or deionized water are sized mixing, quality liquid-solid ratio is 6:1, slowly add under stirring condition
Enter the sodium hydroxide solution that 2L concentration is 1mol/L, charging is passed through air, air capacity 0.3M simultaneously3/ h, charging reaction time
25h, 70 DEG C of reaction temperature continues to react 4h after adding material, is filtered after the completion of reaction, washed, then through being dried to obtain average grain diameter
It is 5.8 μm of heavy mangano-manganic oxide, product tap density 2.15g/cm3, Mn contents 71.56%, sulfate radical content 0.018%.
Embodiment 2
Manganese chloride is dissolved in pure water or deionized water is configured to the manganese chloride solution that 1L concentration is 1mol/L, sodium oxalate is used
Pure water or deionized water are configured to the sodium oxalate solution that 4L concentration is 0.25mol/L, under agitation add manganese chloride solution
Enter in sodium oxalate solution, keep 60 DEG C of reaction temperature, feed time 100min adds the follow-up continuous insulation reaction 40min of material, instead
Filtering, washing, obtain manganese oxalate solid after the completion of answering.
Above-mentioned manganese oxalate solid pure water or deionized water are sized mixing, quality liquid-solid ratio is 7:1, slowly add under stirring condition
Enter the sodium hydroxide solution that 0.5L concentration is 4mol/L, charging is passed through air, air capacity 0.1M simultaneously3/ h, charging reaction time
30h, 30 DEG C of reaction temperature continues to react 5h after adding material, is filtered after the completion of reaction, washed, then through being dried to obtain average grain diameter
It is 5.03 μm of heavy mangano-manganic oxide, product tap density 2.08g/cm3, Mn contents 71.60%, sulfate radical content 0.007%.
Embodiment 3
Manganese nitrate is dissolved in pure water or deionized water is configured to the manganese nitrate solution that 0.5L concentration is 2mol/L, by sodium oxalate
The sodium oxalate solution that 4L concentration is 0.25mol/L is configured to pure water or deionized water, under agitation by manganese nitrate solution
It is added in sodium oxalate solution, keeps 65 DEG C of reaction temperature, feed time 50min adds the follow-up continuous insulation reaction 30min of material,
Filtered after the completion of reaction, washed, obtain manganese oxalate solid.
Above-mentioned manganese oxalate solid pure water or deionized water are sized mixing, quality liquid-solid ratio is 5:1, slowly add under stirring condition
Enter the sodium hydroxide solution that 4L concentration is 0.5mol/L, charging is passed through air, air capacity 0.15M simultaneously3/ h, charging reaction time
35h, 35 DEG C of reaction temperature continues to react 3h after adding material, is filtered after the completion of reaction, washed, then through being dried to obtain average grain diameter
It is 5.47 μm of heavy mangano-manganic oxide, product tap density 2.17g/cm3, Mn contents 71.62%, sulfate radical content 0.006%.
Embodiment 4
Manganese chloride is dissolved in pure water or deionized water is configured to the manganese chloride solution that 1L concentration is 1mol/L, sodium oxalate is used
Pure water or deionized water are configured to the sodium oxalate solution that 2.5L concentration is 0.4mol/L, under agitation add manganese chloride solution
Enter in sodium oxalate solution, keep 90 DEG C of reaction temperature, feed time 10min adds the follow-up continuous insulation reaction 60min of material, instead
Filtering, washing, obtain manganese oxalate solid after the completion of answering.
Above-mentioned manganese oxalate solid pure water or deionized water are sized mixing, quality liquid-solid ratio is 10:1, it is slow under stirring condition
It is the sodium hydroxide solution of 3mol/L to add 0.67L concentration, and charging is passed through air, air capacity 0.2M simultaneously3/ h, during charging reaction
Between 40h, 40 DEG C of reaction temperature continues to react 5h after adding material, is filtered after the completion of reaction, washing, then through being dried to obtain average grain
Footpath is 6.0 μm of heavy mangano-manganic oxide, product tap density 2.21g/cm3, Mn contents 71.66%, sulfate radical content
0.009%。
Embodiment 5
Manganese sulfate is dissolved in pure water or deionized water is configured to the manganese sulfate solution that 0.67L concentration is 1.5mol/L, will be real
Sodium oxalate pure water or deionized water obtained by reaction are configured to the sodium oxalate solution that 5L concentration is 0.2mol/L in applying example 4, are stirring
Manganese sulfate solution is added in sodium oxalate solution under the conditions of mixing, keeps 40 DEG C of reaction temperature, feed time 30min adds material
Follow-up continuous insulation reaction 50min, filters after the completion of reaction, washs, and obtains manganese oxalate solid.
Above-mentioned manganese oxalate solid pure water or deionized water are sized mixing, quality liquid-solid ratio is 8:1, slowly add under stirring condition
Enter the sodium hydroxide solution that 1L concentration is 2mol/L, charging is passed through air, air capacity 0.4M simultaneously3/ h, charging reaction time
40h, 90 DEG C of reaction temperature continues to react 4h after adding material, is filtered after the completion of reaction, washed, then through being dried to obtain average grain diameter
It is 5.51 μm of heavy mangano-manganic oxide, product tap density 2.09g/cm3, Mn contents 71.81%, sulfate radical content 0.018%.
Embodiment 6
Manganese sulfate is dissolved in pure water or deionized water is configured to the manganese sulfate solution that 1.33L concentration is 0.75mol/L, by grass
Sour sodium pure water or deionized water are configured to the sodium oxalate solution that 3.33L concentration is 0.33mol/L, under agitation by sulfuric acid
Manganese solution is added in sodium oxalate solution, keeps 80 DEG C of reaction temperature, and feed time 120min adds the follow-up continuous insulation reaction of material
40min, filters after the completion of reaction, washs, and obtains manganese oxalate solid.
Above-mentioned manganese oxalate solid pure water or deionized water are sized mixing, quality liquid-solid ratio is 6:1, slowly add under stirring condition
Enter the sodium hydroxide solution that 0.4L concentration is 5mol/L, charging is passed through air, air capacity 0.5M simultaneously3/ h, charging reaction time
35h, 80 DEG C of reaction temperature continues to react 6h after adding material, is filtered after the completion of reaction, washed, then through being dried to obtain average grain diameter
It is 5.78 μm of heavy mangano-manganic oxide, product tap density 2.22g/cm3, Mn contents 71.72%, sulfate radical content 0.020%.
Embodiment 7
Manganese nitrate is dissolved in pure water or deionized water is configured to the manganese nitrate solution that 1.25L concentration is 0.8mol/L, by grass
Sour sodium pure water or deionized water are configured to the sodium oxalate solution that 4L concentration is 0.25mol/L, under agitation by manganese nitrate
Solution is added in sodium oxalate solution, keeps 55 DEG C of reaction temperature, and feed time 80min adds the follow-up continuous insulation reaction of material
30min, filters after the completion of reaction, washs, and obtains manganese oxalate solid.
Above-mentioned manganese oxalate solid pure water or deionized water are sized mixing, quality liquid-solid ratio is 5:1, slowly add under stirring condition
Enter the sodium hydroxide solution that 2L concentration is 1mol/L, charging is passed through air, air capacity 0.45M simultaneously3/ h, charging reaction time
30h, 70 DEG C of reaction temperature continues to react 4h after adding material, is filtered after the completion of reaction, washed, then through being dried to obtain average grain diameter
It is 5.33 μm of heavy mangano-manganic oxide, product tap density 2.15g/cm3, Mn contents 71.53%, sulfate radical content 0.005%.
Embodiment 8
Manganese sulfate is dissolved in pure water or deionized water is configured to the manganese sulfate solution that 0.83L concentration is 1.2mol/L, by grass
Sour sodium pure water or deionized water are configured to the sodium oxalate solution that 2.5L concentration is 0.4mol/L, under agitation by manganese sulfate
Solution is added in sodium oxalate solution, keeps 85 DEG C of reaction temperature, and feed time 20min adds the follow-up continuous insulation reaction of material
40min, filters after the completion of reaction, washs, and obtains manganese oxalate solid.
Above-mentioned manganese oxalate solid pure water or deionized water are sized mixing, quality liquid-solid ratio is 7:1, slowly add under stirring condition
Enter the sodium hydroxide solution that 1L concentration is 2mol/L, charging is passed through air, air capacity 0.3M simultaneously3/ h, charging reaction time
25h, 40 DEG C of reaction temperature continues to react 5h after adding material, is filtered after the completion of reaction, washed, then through being dried to obtain average grain diameter
It is 5.52 μm of heavy mangano-manganic oxide, product tap density 2.10g/cm3, Mn contents 71.50%, sulfate radical content 0.017%.
Embodiment 9
Manganese chloride is dissolved in pure water or deionized water is configured to the manganese chloride solution that 0.625L concentration is 1.6mol/L, will be real
Sodium oxalate pure water or deionized water obtained by reaction are configured to the sodium oxalate solution that 5L concentration is 0.2mol/L in applying example 8, are stirring
Manganese chloride solution is added in sodium oxalate solution under the conditions of mixing, keeps 70 DEG C of reaction temperature, feed time 50min adds material
Follow-up continuous insulation reaction 50min, filters after the completion of reaction, washs, and obtains manganese oxalate solid.
Above-mentioned manganese oxalate solid pure water or deionized water are sized mixing, quality liquid-solid ratio is 6:1, slowly add under stirring condition
Enter the sodium hydroxide solution that 4L concentration is 0.5mol/L, charging is passed through air, air capacity 0.2M simultaneously3/ h, charging reaction time
40h, 60 DEG C of reaction temperature continues to react 3h after adding material, is filtered after the completion of reaction, washed, then through being dried to obtain average grain diameter
It is 5.74 μm of heavy mangano-manganic oxide, product tap density 2.18g/cm3, Mn contents 71.61%, sulfate radical content 0.008%.
Embodiment 10
Manganese sulfate is dissolved in pure water or deionized water is configured to the manganese sulfate solution that 2L concentration is 0.5mol/L, by sodium oxalate
The sodium oxalate solution that 5L concentration is 0.2mol/L is configured to pure water or deionized water, under agitation adds manganese sulfate solution
Enter in sodium oxalate solution, keep 50 DEG C of reaction temperature, feed time 60min adds the follow-up continuous insulation reaction 60min of material, instead
Filtering, washing, obtain manganese oxalate solid after the completion of answering.
Above-mentioned manganese oxalate solid pure water or deionized water are sized mixing, quality liquid-solid ratio is 7:1, slowly add under stirring condition
Enter the sodium hydroxide solution that 2L concentration is 1mol/L, charging is passed through air, air capacity 0.25M simultaneously3/ h, charging reaction time
35h, 50 DEG C of reaction temperature continues to react 4h after adding material, is filtered after the completion of reaction, washed, then through being dried to obtain average grain diameter
It is 5.65 μm of heavy mangano-manganic oxide, product tap density 2.09g/cm3, Mn contents 71.53%, sulfate radical content 0.016%.
Claims (3)
1. a kind of preparation method of heavy mangano-manganic oxide, it is characterised in that first with pure water or deionized water by soluble bivalent manganese
Salt dissolving is configured to manganese salt solution, sodium oxalate dissolving is configured to sodium oxalate solution, NaOH dissolving is configured into hydroxide
Sodium solution, then manganese salt solution and sodium oxalate solution carry out precipitation reaction generation solid oxalic acid manganese, will with water after filtering, washing
Solid oxalic acid manganese is deployed into manganese oxalate slurries, then converts manganese oxalate toward being slowly added dropwise sodium hydroxide solution in manganese oxalate slurries
Into manganous hydroxide, it is 6.5~7.5 to control the pH value of reaction system, and being passed through air while sodium hydroxide solution is added dropwise is carried out
Oxidation reaction, heavy mangano-manganic oxide is oxidized to by manganous hydroxide, is filtered after the completion of oxidation reaction, washed, dried, that is, obtain weight
Matter mangano-manganic oxide product, chemical equation is：
Mn2++Na2C2O4=MnC2O4+2Na+
MnC2O4+2NaOH=Mn(OH)2+Na2C2O4
6Mn(OH)2+ O2=2Mn3O4+6H2O。
2. the preparation method of heavy mangano-manganic oxide according to claim 1, it is characterised in that comprise the following steps：
Step one：By soluble manganous salt pure water or deionized water dissolving, the manganese salt solution of 0.5~2mol/L is configured to；
Sodium oxalate pure water or deionized water dissolving are configured to the sodium oxalate solution of 0.2~0.4mol/L；By NaOH pure water
Or deionized water dissolving is configured to the sodium hydroxide solution of 0.5~5mol/L；
Step 2：The manganese salt solution that step one is obtained is added in sodium oxalate solution, by manganese ion and the mol ratio of sodium oxalate
Ratio for 1: 1 feeds intake and carries out precipitation reaction, and controlling reaction temperature is 40 DEG C~90 DEG C, and manganese salt solution feed time 10~
120min, adds 30~60min of insulation reaction after material, is filtered after the completion of reaction, washed, and obtains solid oxalic acid manganese；
Step 3：Step 2 gained solid oxalic acid manganese pure water or deionized water are slurried, the matter of solid oxalic acid manganese and water
Amount liquid-solid ratio is 5~10:1, under agitation toward being slowly added continuously the hydrogen-oxygen that step one is prepared in manganese oxalate slurries
Change sodium solution, manganese oxalate is changed into manganous hydroxide, the by-product sodium oxalate solution that manganese oxalate and NaOH react enters step
Two recycle, and NaOH is 2: 1 with the molar ratio of manganese oxalate, and it is 6.5~7.5, hydrogen to control the pH value of reaction system
20~40h of sodium hydroxide solution charging reaction time, 30 DEG C~90 DEG C of reaction temperature is passed through while sodium hydroxide solution is added dropwise
Air carries out oxidation reaction, and manganous hydroxide is oxidized into heavy mangano-manganic oxide, and air mass flow is 0.1~0.5M3/ h, material is complete
Portion continues to react 3~6h after adding, and is filtered after the completion of oxidation reaction, washed, dried, that is, it is 5 ~ 6 μm, jolt ramming to obtain average grain diameter
Density is more than 2.0g/cm3, Mn contents be more than 71.5%, sulfate radical content less than 0.02% heavy mangano-manganic oxide product.
3. the preparation method of heavy mangano-manganic oxide according to claim 1 or claim 2, it is characterised in that described soluble divalence
Manganese salt is any one in manganese sulfate or manganese nitrate, manganese chloride；Sodium oxalate is the industrial ethanedioic acid sodium of main content 99.5%；Hydrogen-oxygen
Change the industrial solid NaOH that sodium is main content 96%.
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| CN108585050B (en) * | 2018-07-19 | 2020-03-20 | 郝新丽 | Low-temperature green synthesis method of manganous-manganic oxide nanoring |
| CN110776015A (en) * | 2019-11-05 | 2020-02-11 | 江西智锂科技有限公司 | Synthesis method of battery-grade trimanganese tetroxide |
| CN112607789A (en) * | 2020-12-15 | 2021-04-06 | 中南大学 | Process for recovering valuable metals and regenerating anode materials of waste lithium ion batteries |
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| CN113387392A (en) * | 2021-06-09 | 2021-09-14 | 南昌大学 | Preparation method of sodium manganese oxide and application of sodium manganese oxide in super capacitor |
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